US4755541A - Substituted benzophenones and their liquid mixtures suitable for use as photopolymerization initiators - Google Patents

Substituted benzophenones and their liquid mixtures suitable for use as photopolymerization initiators Download PDF

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US4755541A
US4755541A US06/886,929 US88692986A US4755541A US 4755541 A US4755541 A US 4755541A US 88692986 A US88692986 A US 88692986A US 4755541 A US4755541 A US 4755541A
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benzophenone
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hydrogen
alkyl
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Giuseppe Li Bassi
Luciano Cadona
Carlo Nicora
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Lamberti SpA
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents

Definitions

  • This invention relates to the use of systems comprising substituted benzophenones and their liquid mixtures as photopolymerisation initiators for ethylenically unsaturated compounds.
  • Ethylenically unsaturated compounds and in particular acrylic and methacrylic acid derivatives can be polymerised by irradiation with ultraviolet light of wavelength between 200 and 450 nm in the presence of photoinitiator systems formed from:
  • (B) a donor of hydrogen or substances which determine the formation of a labile photochemical complex with the carbonyl compound (A), such as alcohols, tertiary amines or ethers having available hydrogens on the carbon adjacent to the heteroatom.
  • benzophenones which form these photoinitiator systems are benzophenone itself which is the most widely used, 4,4'-bis-dimethyl (or diethyl) aminobenzophenone (Michler ketone), which is very efficient in pigmented systems, 4-hydroxybenzophenone condensed with ethylne oxide and esterified with acrylic acid, which has the advantage of being liquid and copolymerisable, 2-carbomethoxybenzophenone, 3,3',4,4'-benzophenonetetracarboxylic acid esters etc. As many of these products are solid, they are difficult to incorporate into the photopolymerisable systems, or have a photochemical efficiency which is less than benzophenone itself.
  • systems consisting of:
  • R signifies linear or branched C 1 -C 12 alkyl possibly substituted with one or more phenyl, chlorine, bromine, C 1 -C 12 alkoxy, ArO--, ArSO--, ArSO 2 --, C 1 -C 12 alkylsulphinyl or C 1 -C 12 alkylsulphonyl groups; or --SO 3 H or C 1 -C 12 dialkylamino, respectively as free acids or bases or salified with organic or inorganic bases; C 1 -C 12 alkoxy; or ArO---
  • R 1 , R 2 which can be equal or different, each independently have the same meaning as R or represent hydrogen or a bridge of carbon atoms with Ar or R 3 or R 4 possibly comprising heteroatoms
  • R 3 , R 4 which can be equal or different, each independently represent hydrogen, linear or branched C 1 -C 12 alkyl, phenyl, chlorine, bromine, --SO 3 H possibly salified with organic or inorganic bases, or ArCO--
  • AR represents a C 6 -C 10 aryl either non-substituted or carrying one or more substitutes of the halogen, C 1 -C 12 alkyl, phenyl, C 1 -C 4 alkoxy, C 3 -C 6 cycloalkoxy, phenoxy, --COOH, C 1 -C 5 alkoxycarbonyl, benzoyl, C 1 -C 5 dialkylamino, C 1 -C 5 alkylthio, alkylsulphinyl, alkylsulphonyl, arylthio, arylsulphinyl and arylsulphonyl group; or 2,3 or 4-pyridyl; or a furan or thiopene residue
  • (B) an organic tertiary amine of aliphatic type, or an ester of p-dimethylaminobenzoic acid or 4,4'-bis-(C 1 -C 5 dialkylamino) benzophenone, or single or polymeric ethers of primary or secondary alcohols or glycols or primary or secondary aliphatic alcohols or in any event donors of hydrogen or substances which determine the formation of labile chemical complexes, can be used in the photoinitiated polymerisation of ethylenically unsaturated compounds, and in particular of acrylic and methacrylic acid derivatives, with a photochemical efficiency considerably greater than that of analogous systems containing the currently used benzophenones indicated heretofore.
  • Preferred systems for use according to the present invention are those consisting of:
  • R, R 1 , R 2 which can be equal or different, each independently signify C 1 -C 4 alkyl
  • R 3 , R 4 which can be equal or different, each independently signify hydrogen, C 1 -C 4 alkyl, or --SO 3 H possibly salified with organic or inorganic bases,
  • Ar signifies phenyl, possibly substituted with one or more C 1 -C 4 alkyl, Cl, Br or C 1 -C 4 alkylthio groups
  • liquid mixtures of compounds of formula I and benzophenone are those with molar ratios of between 0.1 and 10.
  • liquid mixtures of compounds of formula I and benzophenone are those of 2,4,6-trimethylbenzophenone and benzophenone in molar ratios of between 1 and 1.3 having a pour point less than 0° C.
  • Particularly preferred compounds of type B are single polymeric derivatives of aliphatic alkanolamines, esters of p-dialkylaminobenzoic acid, and aliphatic alcohols and glycols possibly carrying acrylic saturations or included in macromolecular structures.
  • the photopolymerisable compounds with which the photoinitiator systems according to the present invention can be advantageously used are di, tri, tetra or polyfunctional monomers and oligomers of acrylic or methacrylic type, such as esters or amides.
  • Photopolymerisable oligomers and prepolymers are represented most commonly by polyester, polyether, polyurethane, acrylic, epoxy and silicone resins containing acrylic or methacrylic functionalities.
  • Those mixtures useful in the art are those formed from the aforesaid monomers and oligomers in possible combination with pigments, fillers, thermal stabilisers, light stabilisers, antioxidants, paraffins etc., various auxiliaries such as anti-foaming agents, dispersants etc.
  • the co-use of other photoinitiators such as benzyl ketals, benzoin ethers, thioxanthones etc. is also possible.
  • Photopolymerisable mixtures containing the photoinitiator systems according to the present invention can be used as coatings for wood, metal, paper, fabrics, plastics materials, fibreglass, rubber; printing inks, adhesives and sealants; masses for fabricating printing plates or silk-screen matrices; masses for fabricating structural materials.
  • the photopolymerisation process can use medium, low or high pressure mercury vapour lamps, superactinic lamps or lamps specially designed to obtain high radiation intensity at wavelengths between 250 and 450 nm.
  • the photoinitiator systems according to the present invention are used in a quantity of between 0.1 and 15% by weight of the photopolymerisable mixture, and preferably between 0.5 and 10% by weight.
  • the ratio of component A to component B can vary between 0.1 and 10 but values of between 0.5 and 1.5 are preferred.
  • liquid mixtures of compounds of formula I with benzophenone are used, in addition to the stated advantages the preparation of photopolymerisable mixtures takes less mixing time and lower temperatures can be used. In addition the fact that a liquid photoinitiator is used helps to keep the viscosity low and allows co-solubilisation of components which would otherwise be more difficult to dissolve.
  • TMB 2,4,6-trimethylbenzophenone - metastable liquid, B.P. 189° C. (17 mmHg) or crystalline solid with M.P. 35.5° C., IR spectrum (KBr) : 1670, 1270, 917, 710 cm -1 .
  • TEB 2,4,6-triethylbenzophenone - liquid, B.P. 210°-220° C. (40 mmHg), IR spectrum (liquid film) : 1660, 1270, 925, 865, 705 cm -1 .
  • TIPD 2,4,6-triisopropylbenzophenone - crystalline solid, M.P. 98°-99° C., IR spectrum (KBr) : 1665, 1250, 950, 930, 880, 725 cm -1 .
  • TMOB 2,4,6-trimethoxybenzophenone - crystalline solid, M.P. 112°-113° C., IR spectrum (KBr) : 1660, 1600, 1585, 1125, 810 cm -1 .
  • MDEA N-methyldiethanolamine - liquid.
  • the photo-crosslinkable mixtures having the composition indicated in the individual examples given hereinafter were applied to a glass plate to a thickness of 50 microns. After exposure to air for 30 seconds the films were irradiated by successive passages at the indicated conveying speed under a medium pressure mercury vapour lamp of the indicated power at a distance of 10 cm from the light source. Sward hardness (ASTM D2134-66) and yellowing (ASTM D1925-63T) were determined.
  • the thermal stability evaluated for photoinitiated mixtures kept in darkness at 60° C., was greater than 30 days for all the photoinitiator systems.
  • Example 2 the operating conditions and results were as follows:
  • Example 3 the operating conditions and results were as follows:
  • Example 4 the operating conditions and results were as follows:
  • Example 5 the operating conditions and results were as follows:

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  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Polymerisation Methods In General (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

As initiators for the photopolymerisation of ethylenically unsaturated compounds, the use of systems consisting of compounds of benzophenone type of formula I ##STR1## in which R, R' and R2 are preferably alkyls of 1-4 carbon atoms, R3 and R4 are preferably hydrogen and Ar is preferably phenyl, in combination with donors of hydrogen or substances which determine the formation of labile photochemical complexes, such as alcohols, ethers and tertiary amines with hydrogen in the alpha position, and the use for the same purpose of mixtures of 2,4,6-trialkylbenzophenones and benzophenone and particularly of a mixture of 2,4,6-trimethylbenzophenone and benzophenone in a molar ratio of 1.155, which has the advantage of being liquid at temperatures exceeding 10° C. and of possessing photochemical activity superior to that of benzophenone.

Description

This invention relates to the use of systems comprising substituted benzophenones and their liquid mixtures as photopolymerisation initiators for ethylenically unsaturated compounds.
Ethylenically unsaturated compounds and in particular acrylic and methacrylic acid derivatives can be polymerised by irradiation with ultraviolet light of wavelength between 200 and 450 nm in the presence of photoinitiator systems formed from:
(A) benzophenone or its derivatives
(B) a donor of hydrogen or substances which determine the formation of a labile photochemical complex with the carbonyl compound (A), such as alcohols, tertiary amines or ethers having available hydrogens on the carbon adjacent to the heteroatom.
Examples of benzophenones which form these photoinitiator systems are benzophenone itself which is the most widely used, 4,4'-bis-dimethyl (or diethyl) aminobenzophenone (Michler ketone), which is very efficient in pigmented systems, 4-hydroxybenzophenone condensed with ethylne oxide and esterified with acrylic acid, which has the advantage of being liquid and copolymerisable, 2-carbomethoxybenzophenone, 3,3',4,4'-benzophenonetetracarboxylic acid esters etc. As many of these products are solid, they are difficult to incorporate into the photopolymerisable systems, or have a photochemical efficiency which is less than benzophenone itself. In accordance with the present invention, we have now surprisingly discovered that systems consisting of:
(A) compounds of formula I ##STR2## in which R signifies linear or branched C1 -C12 alkyl possibly substituted with one or more phenyl, chlorine, bromine, C1 -C12 alkoxy, ArO--, ArSO--, ArSO2 --, C1 -C12 alkylsulphinyl or C1 -C12 alkylsulphonyl groups; or --SO3 H or C1 -C12 dialkylamino, respectively as free acids or bases or salified with organic or inorganic bases; C1 -C12 alkoxy; or ArO--
R1, R2 which can be equal or different, each independently have the same meaning as R or represent hydrogen or a bridge of carbon atoms with Ar or R3 or R4 possibly comprising heteroatoms
R3, R4 which can be equal or different, each independently represent hydrogen, linear or branched C1 -C12 alkyl, phenyl, chlorine, bromine, --SO3 H possibly salified with organic or inorganic bases, or ArCO--
AR represents a C6 -C10 aryl either non-substituted or carrying one or more substitutes of the halogen, C1 -C12 alkyl, phenyl, C1 -C4 alkoxy, C3 -C6 cycloalkoxy, phenoxy, --COOH, C1 -C5 alkoxycarbonyl, benzoyl, C1 -C5 dialkylamino, C1 -C5 alkylthio, alkylsulphinyl, alkylsulphonyl, arylthio, arylsulphinyl and arylsulphonyl group; or 2,3 or 4-pyridyl; or a furan or thiopene residue
(B) an organic tertiary amine of aliphatic type, or an ester of p-dimethylaminobenzoic acid or 4,4'-bis-(C1 -C5 dialkylamino) benzophenone, or single or polymeric ethers of primary or secondary alcohols or glycols or primary or secondary aliphatic alcohols or in any event donors of hydrogen or substances which determine the formation of labile chemical complexes, can be used in the photoinitiated polymerisation of ethylenically unsaturated compounds, and in particular of acrylic and methacrylic acid derivatives, with a photochemical efficiency considerably greater than that of analogous systems containing the currently used benzophenones indicated heretofore.
Further according to the invention, we have also surprisingly found that particular mixtures of benzophenone and compounds of formula I, by virtue of having melting points considerably lower than those of the individual compounds, can be used in the liquid state with considerable practical advantages with regard to their incorporation into the photopolymerisable mixtures, in combination with the compounds of type B indicated heretofore.
Preferred systems for use according to the present invention are those consisting of:
(A) one or more benzophenones of formula I in which
R, R1, R2 which can be equal or different, each independently signify C1 -C4 alkyl,
R3, R4 which can be equal or different, each independently signify hydrogen, C1 -C4 alkyl, or --SO3 H possibly salified with organic or inorganic bases,
Ar signifies phenyl, possibly substituted with one or more C1 -C4 alkyl, Cl, Br or C1 -C4 alkylthio groups
(B) an organic tertiary amine of aliphatic type, or an ester of p-dimethylaminobenzoic acid or 4,4'-bis-(C1 -C5 dialkylamino) benzophenone, or molecules containing single or polymeric derivatives of glycols.
Examples of compounds of formula 1 are:
2,4,6-trimethylbenzophenone
2,4,6-triethylbenzophenone
2,4,6-triisopropylbenzophenone
2,4,6-tritert.butylbenzophenone
2,4,6-trimethoxybenzophenone
2,3,4,5,6-pentamethylbenzophenone
sodium 2,4,6-trimethylbenzophenone-3-sulphonate
4-(2,4,6-trimethylbenzoyl)pyridine
2-(2,4,6-trimethylbenzoyl)pyridine.
Preferred as liquid mixtures of compounds of formula I and benzophenone are those with molar ratios of between 0.1 and 10.
Particularly preferred as liquid mixtures of compounds of formula I and benzophenone are those of 2,4,6-trimethylbenzophenone and benzophenone in molar ratios of between 1 and 1.3 having a pour point less than 0° C.
Particularly preferred compounds of type B are single polymeric derivatives of aliphatic alkanolamines, esters of p-dialkylaminobenzoic acid, and aliphatic alcohols and glycols possibly carrying acrylic saturations or included in macromolecular structures.
Compounds of formula I are known from the scientific literature and are normally obtained by Friedel-Crafts acylation (Houben Weyl, Methoden der Organischen Chemie, Band VII/2a, Teil 1, pag. 164-233) in accordance with the two following alternatives: ##STR3## where cat. signifies a Friedel-Crafts catalyst. For example 2,4,6-trimethylbenzophenone has been obtained by acylation of mesitylene with benzoyl chloride in the presence of anhydrous aluminium chloride [Louise, Annales del Chemie, 6 (6) 202; H. O. House et al., J. Org. Chem., 41, 3083 (1976)].
Although there are numerous publications in the literature on the photochemistry and photophysics of the compounds of formula I, and in particular of 2,4,6-trialkylbenzophenones [Y. Kitaura et al., Tetrahedron, 27 1597 (1971) - Y. Ito et al., J. Am. Chem. Soc. 102, 5917 (1980), ibid. 105, 1590 (1983), J. Org. Chem., 46, 4359 (1981) - G. Porter et al., J. Chem. Soc. (A) 3772 (1971), Chem. Comm., 1372 (1970)] there is no reference to their use as polymerisation photoinitiators.
The photopolymerisable compounds with which the photoinitiator systems according to the present invention can be advantageously used are di, tri, tetra or polyfunctional monomers and oligomers of acrylic or methacrylic type, such as esters or amides.
Photopolymerisable oligomers and prepolymers are represented most commonly by polyester, polyether, polyurethane, acrylic, epoxy and silicone resins containing acrylic or methacrylic functionalities. Those mixtures useful in the art are those formed from the aforesaid monomers and oligomers in possible combination with pigments, fillers, thermal stabilisers, light stabilisers, antioxidants, paraffins etc., various auxiliaries such as anti-foaming agents, dispersants etc. The co-use of other photoinitiators such as benzyl ketals, benzoin ethers, thioxanthones etc. is also possible.
Photopolymerisable mixtures containing the photoinitiator systems according to the present invention can be used as coatings for wood, metal, paper, fabrics, plastics materials, fibreglass, rubber; printing inks, adhesives and sealants; masses for fabricating printing plates or silk-screen matrices; masses for fabricating structural materials.
With regard to light sources, the photopolymerisation process can use medium, low or high pressure mercury vapour lamps, superactinic lamps or lamps specially designed to obtain high radiation intensity at wavelengths between 250 and 450 nm.
The photoinitiator systems according to the present invention are used in a quantity of between 0.1 and 15% by weight of the photopolymerisable mixture, and preferably between 0.5 and 10% by weight. The ratio of component A to component B can vary between 0.1 and 10 but values of between 0.5 and 1.5 are preferred.
When the compounds of formula I are used as the benzophenone system of type A, three advantages are obtained over the use of benzophenone itself, namely better photochemical efficiency and less film coloration and odour.
When liquid mixtures of compounds of formula I with benzophenone are used, in addition to the stated advantages the preparation of photopolymerisable mixtures takes less mixing time and lower temperatures can be used. In addition the fact that a liquid photoinitiator is used helps to keep the viscosity low and allows co-solubilisation of components which would otherwise be more difficult to dissolve.
The following examples illustrate the invention in greater detail, but without limiting it (the parts are by weight).
The benzophenones used are indicated by abbreviations and have the following characteristics:
BF=benzophenone - crystalline solid, M.P. 49° C., IR spectrum (KBr) : 1655, 1275, 695, 633 cm-1.
TMB=2,4,6-trimethylbenzophenone - metastable liquid, B.P. 189° C. (17 mmHg) or crystalline solid with M.P. 35.5° C., IR spectrum (KBr) : 1670, 1270, 917, 710 cm-1.
TEB=2,4,6-triethylbenzophenone - liquid, B.P. 210°-220° C. (40 mmHg), IR spectrum (liquid film) : 1660, 1270, 925, 865, 705 cm-1.
TIPD=2,4,6-triisopropylbenzophenone - crystalline solid, M.P. 98°-99° C., IR spectrum (KBr) : 1665, 1250, 950, 930, 880, 725 cm-1.
PMB=2,3,4,5,6-pentamethylbenzophenone - crystalline solid, M.P. 134°-135° C., IR spectrum (KBr) : 1670, 1210, 890, 705 cm-1.
TMOB=2,4,6-trimethoxybenzophenone - crystalline solid, M.P. 112°-113° C., IR spectrum (KBr) : 1660, 1600, 1585, 1125, 810 cm-1.
MDEA=N-methyldiethanolamine - liquid.
EXAMPLE 1 Eutectic mixture of 2,4,6-trimethylbenzophenone and benzophenone (BF/TMB)
585 g of 2,4,6-trimethylbenzophenone (M.P. 35.5° C.) are heated to 45° C., 415 g of benzophenone (M.P. 49° C.) are added, and after agitation for 15 minutes the mixture is cooled to 20° C. A composition is obtained (molar ratio TMB/BF=1.155) having the following characteristics; IR spectrum (liquid film): 1660, 1270, 905, 700 cm-1 ; clear liquid up to 10° C.; pour point (ASTM D97/66) less than -10° C.; Brookfield viscosity RVT 1/20 rpm=55 mPas at 20° C., e=145 mPas at 10° C.
EXAMPLES 2 to 5
The photo-crosslinkable mixtures having the composition indicated in the individual examples given hereinafter were applied to a glass plate to a thickness of 50 microns. After exposure to air for 30 seconds the films were irradiated by successive passages at the indicated conveying speed under a medium pressure mercury vapour lamp of the indicated power at a distance of 10 cm from the light source. Sward hardness (ASTM D2134-66) and yellowing (ASTM D1925-63T) were determined.
The thermal stability, evaluated for photoinitiated mixtures kept in darkness at 60° C., was greater than 30 days for all the photoinitiator systems.
In Example 2, the operating conditions and results were as follows:
__________________________________________________________________________
Photo-crosslinkable                                                       
                 Laromer ® LR 8496 (acrylated aliphatic               
                                     95-93                                
composition      epoxy resin BASF) (R)                                    
                 MDEA                1-3                                  
                 Benzophenone compound (50% solution                      
                                     4                                    
                 in 1,6-hexanedioldiacrylate) (A)                         
Lamp power       40 W/cm                                                  
Conveying speed  20 m/min.                                                
__________________________________________________________________________
MDEA      R   Film tacki-                                                 
parts     parts                                                           
              ness after                                                  
                     Sward hardness after                                 
                                       Yellowing Index                    
A    by wt                                                                
          by wt                                                           
              1 passage                                                   
                     2 passages                                           
                           3 passages                                     
                                 4 passages                               
                                       after 4 passages                   
__________________________________________________________________________
BF (a)                                                                    
     1    95  liquid 6     10    14    5                                  
     2    94  tacky  8     12    14    6                                  
     3    93  slightly tacky                                              
                     10    10    14    6                                  
TMB  1    95  tacky  8     12    16    3                                  
     2    94  slightly tacky                                              
                     10    12    16    3                                  
     3    93  dry    10    12    16    3                                  
BF/TMB                                                                    
     1    95  slightly tacky                                              
                     8     12    14    4                                  
     2    94  dry    8     12    16    4                                  
     3    93  dry    10    12    16    4                                  
__________________________________________________________________________
 (a) BF was used for comparison purposes
In Example 3, the operating conditions and results were as follows:
__________________________________________________________________________
Photo-crosslinkable                                                       
                 Laromer ® EA 81 (acrylated aromatic                  
                                    86                                    
composition      epoxy resin BASF) (R)                                    
                 1,6-hexanediol diacrylate (HDDA)                         
                                       0-12.25                            
                 benzophenone compound (50% solution                      
                                    1-8                                   
                 in HDDA) (B)                                             
                 MDEA               0.75-6                                
Lamp power       40 W/cm                                                  
Conveying speed  20 m/min.                                                
__________________________________________________________________________
B        MDEA HDDA                                                        
parts    parts                                                            
              parts                                                       
                   Sward hardness after                                   
B    by wt                                                                
         by wt                                                            
              by wt                                                       
                   1 passage                                              
                        2 passages                                        
                              3 passages                                  
                                    4 passages                            
                                          5 passages                      
__________________________________________________________________________
BF (a)                                                                    
     1   0.75 12.25                                                       
                   tacky                                                  
                         2     6     6     8                              
     2   1.5  10.50                                                       
                   12   18    20    24    24                              
     4   3.0  7.0  12   20    24    26    30                              
     8   6.0  --    8   16    20    26    28                              
TMB  1   0.76 12.26                                                       
                    8   10    12    12    12                              
     2   1.5  12.50                                                       
                   16   22    22    28    28                              
     4   3.0  7.0  14   24    28    32    32                              
     8   6.0  --   12   22    26    26    30                              
BF/TMB                                                                    
     1   0.75 12.25                                                       
                    4    8    10    10    12                              
     2   1.5  10.50                                                       
                   12   18    22    26    26                              
     4   3.0  7.0  14   22    28    30    32                              
     8   6.0  --   12   20    12    26    28                              
PMB  2   1.5  10.50                                                       
                   --   22    22    26    26                              
TIPB 2   1.5  10.50                                                       
                   --   18    22    24    26                              
TMOB 2   1.5  10.50                                                       
                   --   16    20    22    24                              
__________________________________________________________________________
 (a) BF was used for comparison purposes
In Example 4, the operating conditions and results were as follows:
______________________________________                                    
Photo-crosslinkable                                                       
             Laromer ® EA 81  86                                      
composition  benzophenone compound (18.2%                                 
                                  11                                      
             solution in vinylpyrrolidone) (B)                            
             MDEA                  3                                      
Lamp power   40 W/cm                                                      
Conveying speed                                                           
             20 m/min.                                                    
______________________________________                                    
Sward Hardness after:                                                     
       1 passage 2 passages                                               
                           3 passages                                     
                                    4 passages                            
______________________________________                                    
BF (a) 22        30        32       38                                    
TMB    24        32        38       40                                    
TIPB   18        32        38       40                                    
PMB    20        30        36       38                                    
TEB    26        28        34       38                                    
______________________________________                                    
 (a) BF was used for comparison purposes
In Example 5, the operating conditions and results were as follows:
______________________________________                                    
Photo-crosslinkable                                                       
            Laromer ® 55 F (acrylated polyester                       
                                  100                                     
composition resin BASF)                                                   
            benzophenone compound (A)                                     
                                   2                                      
            Silicone Dow DC 190 (20% solution                             
                                  0.2                                     
            in xylene)                                                    
Film thickness                                                            
            500 microns                                                   
Lamp power  80 W/cm                                                       
______________________________________                                    
             Yellowing index of                                           
             crosslinked film after:                                      
                              10 passages                                 
A              1 passage at 3.5 m/min                                     
                              at 1 m/min                                  
______________________________________                                    
BF (a)         2              15                                          
TMB            2              10                                          
2,2-dimethoxy-2-                                                          
               10             20                                          
phenylacetophenone (b)                                                    
1-benzoylcyclohexanol (b)                                                 
               5              12                                          
______________________________________                                    
 (A) used for comparison purposes                                         
 (b) nonbenzophenone compounds used for comparion purposes.

Claims (7)

We claim:
1. Systems useful as initiators for the photopolymerization of ethylenically unsaturated compounds, comprising:
(a) a mixture of benzophenone and at least one benzophenone of formula I ##STR4## in which R, R1, R2, which can be the same or different, each independently represent a C1 -C4 alkyl,
R3, R4, which can be the same or different, each independently represent a member selected from the group consisting of hydrogen, C1 -C4 alkyl, --SO3 H and SO3 H salified with organic or inorganic bases,
Ar represents a member selected from the group consisting of phenyl, unsubstituted or substituted with one or more C1 -C4 alkyl, Cl, Br, and C1 -C4 alkylthio; and
(b) at least one member selected from the group consisting of an organic tertiary amine of aliphatic type, an ester of p-dimethylaminobenzoic acid, 4,4'-bis-(C1 -C6 dialkylamino) benzophenone.
2. Systems according to claim 1, wherein the benzophenone of formula (I) is 2,4,6-trimethylbenzophenone.
3. System according to claim 1, wherein the benzophenone of formula (I) is 2,4,6-triethylbenzophenone.
4. System according to claim 1, wherein the benzophenone of formula (I) is 2,4,6-triisopropyl-benzophenone.
5. System according to claim 1, wherein the benzophenone of formula (I) is 2,3,4,5,6-pentamethylbenzophenone.
6. Systems according to claim 1, wherein the benzophenone of formula (I) is mixed with benzophenone in a molecular ratio of from 10:1 to 1:10.
7. A photocurable composition comprising at least one photopolymerizable ethylenically unsaturated compound and the composition of claim 1 as photoinitiator therefor.
US06/886,929 1985-07-23 1986-07-18 Substituted benzophenones and their liquid mixtures suitable for use as photopolymerization initiators Expired - Lifetime US4755541A (en)

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IT21684A/85 1985-07-23
IT8521684A IT1187703B (en) 1985-07-23 1985-07-23 SUBSTITUTED BENZOPHENONES AND THEIR LIQUID MIXTURES, SUITABLE FOR USE AS PHOTOPOLYMERIZATION INITIATORS

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US20060160915A1 (en) * 2003-02-20 2006-07-20 Andre Fuchs Photocurable compositions
CN102351676A (en) * 2011-08-19 2012-02-15 滨海锦翔化学助剂有限公司 Method for preparing polymer hydroxy ketone photoinitiators

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CN102351676A (en) * 2011-08-19 2012-02-15 滨海锦翔化学助剂有限公司 Method for preparing polymer hydroxy ketone photoinitiators

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JPS6232104A (en) 1987-02-12
IT8521684A0 (en) 1985-07-23
DE3671233D1 (en) 1990-06-21
EP0209831B1 (en) 1990-05-16
IT1187703B (en) 1987-12-23
EP0209831A3 (en) 1987-04-22
EP0209831A2 (en) 1987-01-28

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